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Glycerol composition.

Just a new thread to keep this subject separate so not to confuse things.

I have 'cracked' glycerol with conc sulphuric acid several times. The result is always similar. The glycerol is ex-process or has been used to pre wash oil. The process did not use any method to dry the methoxide (imisides, asm, other)

The top layer of FFA's is always about 1/3 of the total volume. This top layer was the soap contained in the glycerol, now hydrolysed by the acid.

A friend of mine who used to make bio commercially from glycerol would buy his feedstock from large biodiesel producers. He would have it delivered in tankers, 27000 litres per go. His yield of FFA's from this glycerol was variable but always around the 35% level.

During our process if our oil is dry and has no or very little titration and our methoxide is dry (ASM, Imisides or whatever) then the amount of soap produced is greatly reduced.

If we can approach a near anhydrous process the glycerol volume can be reduced by up to 1/3 Where has the extra volume gone? - it is in the bio as extra yield, not in the glycerol as soap.

This is an extract from Tillys post telling me I'm talking a load of Ba**s

Hi smithy,
In keeping with the spirit of trying to clear up the many inaccurate and misleading posts you have made, I think this is a good point to clear up this amazing bit of misinformation you posted early in this thread.

Originally Posted by smithy
Anyway just to add, when I tried this method coming up to 3 years ago using Potassium Methoxide dried by using quicklime (CaO) the volume of glycerol recovered after processing was greatly reduced. Glycerol has a variable soap content depending on oil quality, methanol quality and type of catalyst used, but is in the order of 35%. With the dry methoxide there was virtually no potassium soap, so the glycerol volume was about 2/3 of normal.

If this were true, which of course it isn't, that would mean that your byproduct layer (Glycerol) is about 92% pure glycerine.
I have actually pointed this out to you several times over the years but it seemed to make no difference and you continually post these impossible results as being the truth.
-----------------------------------------------------------

Have you somehow miscalculated the amount of glycerine in rapeseed oil Tilly?

Re: Glycerol composition.

Hi smithy,

Originally Posted by smithy

Have you somehow miscalculated the amount of glycerine in rapeseed oil Tilly?

There are 74ml of glycerin in a litre of vegetable oil.
You claimed to have reacted 200 litres of WVO which produced 16 litres of by-product/ glycerol.
The amount of glycerine in 200 litres of WVO would be 74ml x 200= 14800ml= 14.8 litres
Total glycerine content of the by-product /glycerol layer in your reaction would be 14800/16000 of the total amount of by-product= 92.5% of the total volume.

But that was not the most amazing part! You claimed to have performed this single stage reaction using only 24 litres of methanol! That is only 12% methanol!!

Of course the problem is that while you pretend to be performing a single stage reaction on WVO, you are actually performing the second stage reaction on partially reacted biodiesel

Re: Glycerol composition.

As regards moving towards a water free process by drying oil using a glycerol pre-treatment and using predominantly a water free methoxise;

jamesrl (highly regarded on the ok vod forum with his work on 2 stage eductors) reported on 6.12.13 "I never get more than 65 to 70% glycerol of the added methoxide volume"

Richard P reported on biopowered on 27.2.13, talking about his experiances using ASM he said that he reacted 160/170 litre batches. He added around 26 litres of methoxide and got a similar amount of ex process glycerol. After using ASM he added a similar amount of methoxide and produced only 15 litres of glycerol.

Re: Glycerol composition.

Hi smithy,

When a 2 stage reaction is performed such as you do when you perform a first stage reaction with the glycerol pre-treatment, there is by-product/ glycerol produced in both stages.
The amount of by-product/ glycerol produced in each stage is variable depending on many things including, but not limited to, the amount of chemicals used in each stage and the initial titration of the oil.

Because you pretend your glycerol pre-treatment is not a stage of reaction, you do not count the amount of by-product/ glycerol produced in your first stage reaction. The byproduct/ glycerol produced in this first stage reaction is removed along with the glycerol you added to perform this first stage reaction and you pretend the by-product/ glycerol produced in this first stage reaction never existed.
You pretend that the only by-product/ glycerol produced is that which is produced in the second stage reaction.

I assure you that chemical reactions are the same in York England as they are here in sunny ลึก ประเทศอินเด&
What you are doing is not magical, it is only that while you are pretending to be performing a single stage reaction,you are actually performing a 2 stage reaction and only counting the by-product/ glycerol produced in the second stage reaction

Re: Glycerol composition.

Hi Tilly, Don't you get all hyped up with my glycerol pre-treats, don't worry about them, just stay calm.

Hi Everyone on the forum down under that brews bio. Smithy here from blighty. Want to increase your yield? Want to produce less glycerol byproduct?

Make sure your oil is dry, Make sure you have neutralised all the FFA's (doing a glycerol pre-treatment is best)

Make sure you use dry methoxide (use either ASM or 50/50 ASM/KOH or use KOH and dry the methoxide by the Imisides method)

You will find you produce roughly 2/3 of your normal glycerol amount ( the missing 1/3 will be in your processor as bio)

Just a little story here about someone I helped on the UK forum.

His oil titrated at 25ish and his yield was 62 litres of bio from 100 litres of oil using a base/base process. I suggested to him that if he did an enhanced glycerol pre-wash (adding methoxide to the glycerol) it would result in a more efficient process. He tried this and ended up with oil that (from memory titrated at about 5) His process did not result in any significant reduction in chemicals but his yield ended up at 82 litres and (guess what) his glycerol amount reduced by about 20 litres.

So if your oil titrates high and you can't be bothered to do AE then try this, it works really well.

Re: Glycerol composition.

I see you have gone into panic mode.You are always much more entertaining when you are in panic mode.

Originally Posted by smithy

Want to increase your yield? Want to produce less glycerol byproduct?
Make sure you have neutralised all the FFA's (doing a glycerol pre-treatment is best)

But what if they do not have access to glycerol from another brewer that contains plenty of methoxide like you use to perform the glycerol pre-treatment and they are only using 12% methanol in the reaction as you claim you do?
Then what should they do?Wherever are they to get their methoxide rich glycerol that is necessary to perform the glycerol pre-treatment that you pretend does not perform a stage of reaction?

I suggested to him that if he did an enhanced glycerol pre-wash (adding methoxide to the glycerol)

Adding methoxide to the glycerol!!What a brilliant idea!!!
You add EXTRA methoxide to the glycerol that you perform the glycerol pre-wash with and pretend it is not a stage of reaction. Very clever!
I am sure no one will spot the deception

Make sure you use dry methoxide (use either ASM or 50/50 ASM/KOH or use KOH and dry the methoxide by the Imisides method) You will find you produce roughly 2/3 of your normal glycerol amount ( the missing 1/3 will be in your processor as bio)

Let us see how that claim stacks up with the test results DavidS recently posted.
He performed a reaction on a litre of new oil and the methoxide had not been dried.
He achieved a yield of 1039ml of Biodiesel with a glycerol fall out of 121ml.
That gave him a yield of about 103.9% by volume.
Theoretically the maximum yield is about 104% by volume.

Now if he had performed your glycerol prewash first, you claim that would have remove about 1/3 of the volume from the fallout to the biodiesel as extra biodiesel produced. An extra 40ml of biodiesel.
That would gives us a new volume of 1079ml biodiesel for a yield of 107.9% by volume.
But the theoretical maximum yield is only 104% by volume.

IT'S MAGIC!
YOU HAVE DISCOVERED A MAGICAL PROCEDURE!!

That seems to be the story of your life.You often claim to do magical things no one else can do.

"I appreciate your effort here but you consistently get results that no one else can achieve due to unknown circumstances, because of this your results dont hold much weight."

Re: Glycerol composition.

What on earth are you going on about Tilly! Do you think that by posting in larger text people will give you more credit.

The enhanced pre-wash works well with higher titrating oils if for whatever reason AE is not practical. As the FFA's are neutralised in the prescence of glycerol then the excess water from the neutralisation is removed. No water and no ffa's in the oil gives a much better reaction.

The reason with the DavidS tests that he seemed to achieve a good reaction with the undried methoxide was that the reaction had not reached completion. The small amount of dropout in the tube indicates that the sample would have a considerable amount of mono and diglycerides present. This was not so with the dried methoxide sample and also the extra glycerol in the dried sample proves the bio from the undried methoxide still had a way to go to completion.

Re: Glycerol composition.

As the FFA's are neutralised in the prescence of glycerol then the excess water from the neutralisation is removed. No water and no ffa's in the oil gives a much better reaction.

Yes, that is what happens in a first stage reaction.
The FFA's are neutralised in the presence of the methoxide. They are converted into soap and water.
Glycerine and biodiesel is also produced during this first stage reaction.
At the completion of the first stage the soap and water and glycerine are removed while the partially reacted biodiesel produced remains in the reactor. Because you pretend the first stage reaction never happens, you never counted the Soap, water and glycerine produced during this first stage reaction as part of the total byproduct/ glycerol produced during the 2 stage reaction of the oil.
You also never mention the partial conversion of the WVO into biodiesel that occurs in this first stage reaction.

You pretend to do single stage reactions using impossibly small amounts of methanol while producing impossibly small amounts of glycerol.

This is where the magic comes inYou claim to achieve a complete reaction on WVO in a single stage using 12% methanol.
Please explain the magic you employ to achieve a full reaction in a single stage on WVO using only 12% methanol.
I am sure everyone wants to know how you achieve a complete reaction in a single stage using just 12% methanol!

The reason with the DavidS tests that he seemed to achieve a good reaction with the undried methoxide was that the reaction had not reached completion. The small amount of dropout in the tube indicates that the sample would have a considerable amount of mono and diglycerides present. This was not so with the dried methoxide sample and also the extra glycerol in the dried sample proves the bio from the undried methoxide still had a way to go to completion.

You seem confused.
I thought this magical procedure was supposed to reduce glycerol not increase it as you are now saying happens.

Still no magic detected so far, just that you are continually posting false and misleading information

"I appreciate your effort here but you consistently get results that no one else can achieve due to unknown circumstances, because of this your results dont hold much weight."

Re: Glycerol composition.

Question, Does the glycerol pre-treatment produce glycerol.

smithy; Not usually unless the glycerol is enhanced. A normal glycerol pre-treatment using glycerol from the previous reaction usually only serves to reduce the titration value as well as drying the oil and recovering most of the tied up bio in the glycerol.

Question, When you say the glycerol volume is reduced by about 1/3 using an anhydrous process exactly what do you mean.

smithy; Exactly that, for instance when my oil shows a 20% conversion before the 1st reaction then in any case the ex process glycerol volume is going to be less. However adding dry methoxide reduces whatever volume of glycerol that would have been produced by about 1/3
Most of the water unintentionally added to the process is in the methoxide. If using KOH in an average concentration this water level is in the order of 2.6% plus whatever water is in the methanol. So even in a multistage process that % of water is added everytime the methoxide is added.

Question, Do you think there is anything magical about your proceedure.

smithy; Of course not, don't be silly.

Question, Even though only 2 members of this forum are posting to this thread I have heared there are a number of members interested in your work, so why are they not contributing.

smithy; It may well be that they prefer to contact me by PM to avoid the belittlement and hassle that would result.

Question, if that is the case then surely it is counter productive to the forum?

smithy; Indeed it is, all subjects regarding this thread need to be discussed in public, if some members are reluctant to do so because of humiliation it is indeed a sad state of affairs.

Re: Glycerol composition.

Another thought is that we are all sitting back watching the entertainment. A duel between 2 very different people.
I am sure that you will both continue to trade posts and treat each other with respect.

Life is a journey, with problems to solve, lessons to learn, but most of all, experiences to enjoy.